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Remarkable phase-matchable second-harmonic generation realized by strong polarities of [PbSe3] and [GaSe4] functional motifs in PbGa4Se7

化合物PbGa4Se7中[PbSe3]和[GaSe4]功能基元的强极化实现高的相位匹配二次谐波效应

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Abstract

Strong second-harmonic generation (SHG) and phase-matchable capability at specific transmittance windows are crucial to the real application of nonlinear optical crystals. Herein, an efficient strategy of introducing Pb2+ with stereochemically active lone-pair electrons into non-phase-match-able Ga2Se3via enhancing the anisotropy microstructure is first applied to meet phase-matchable SHG intensity requirements, offering a selenide, namely, PbGa4Se7, which is designed and synthesized with a diamond-like anionic framework, where Pb2+ cations reside in a parallel arrangement. As expected, PbGa4Se7 possesses a large SHG coefficient of 3.3 times that of AgGaS2 under the incident laser of 1910 nm. Moreover, PbGa4Se7 displays a high laser-induced damage threshold of 7.0 times that of AgGaS2 at 2090 nm, which originates from the low anisotropy of thermal expansion coefficient (0.36) and suitable optical band gap (2.1 eV). Theoretical calculations demonstrate that the considerable phase-matchable SHG response of PbGa4Se7 can be attributed to the synergies of tetrahedral GaSe4 and pyramid PbSe3 microstructural blocks with additional anisotropy and polarizability.

摘要

二次谐波效应和相位匹配能力对于二阶非线性光学晶体的实际应用至关重要. 在本工作中, 我们通过将具有立体化学活性电子对的Pb2+引入非相位匹配的Ga2Se3, 增强其各向异性和二阶超极化率. 基于以上策略, 我们制备了一种硒化物PbGa4Se7, 其晶体结构由类金刚石阴离子骨架和插入到间隙中的Pb2+组成. 在1910 nm的激光照射下,PbGa4Se7具有大的二次谐波系数(3.3 × AgGaS2); 同时, 其具有低的热膨胀系数各向异性(0.5)和合适的光学带隙(2.1 eV), 在2090 nm激光照射下, 表现出高的激光诱导损伤阈值(7.0 × AgGaS2). PbGa4Se7的相位匹配能力和强二次谐波效应可归因于非线性光学功能基元(四面体GaSe4和金字塔PbSe3结构单元)的协同作用产生了额外的各向异性和极化率.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (21827813, 21921001, 22175172, 22075283, 92161125, and U21A20508) and the Youth Innovation Promotion Association of Chinese Academy of Sciences (2020303 and 2021300).

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Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Zhe-Xiong Zheng  (郑哲雄), Zhi-Xin Qiu  (邱智鑫), Chao-Hong Xie  (谢潮泓), Yang-Ping Zhang  (张阳苹), Xiao-Ming Jiang  (姜小明), Bin-Wen Liu  (刘彬文) & Guo-Cong Guo  (郭国聪)

  2. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, 350108, China

    Xiao-Ming Jiang  (姜小明), Bin-Wen Liu  (刘彬文) & Guo-Cong Guo  (郭国聪)

  3. School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, China

    Zhe-Xiong Zheng  (郑哲雄), Yang-Ping Zhang  (张阳苹) & Guo-Cong Guo  (郭国聪)

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  1. Zhe-Xiong Zheng  (郑哲雄)
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Contributions

Author contributions Zheng ZX performed the experiments, data analyses, and manuscript writing; Xie CH and Zhang YP offered some advice on the manuscript writing. Qiu ZX performed the theoretical analyses; Liu BW and Guo GC guided and supervised the experiments, and revised the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Bin-Wen Liu  (刘彬文) or Guo-Cong Guo  (郭国聪).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Supporting data are available in the online version of the paper.

Zhe-Xiong Zheng received his BE degree of chemical technology from Xiamen University in 2020. He is currently an MS student and focuses on nonlinear optical materials at ShanghaiTech University.

Bin-Wen Liu received his BE degree from Hunan University in 2010 and PhD degree in inorganic chemistry from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences in 2016. Since 2019, he has been working as an associate professor at Fujian Institute of Research on the Structure of Matter. His current research interests include solid-state inorganic chemistry and nonlinear optical materials.

Guo-Cong Guo received his BS degree from Xiamen University in 1986 and PhD degree from The Chinese University of Hong Kong in 1999. Since 2000, he has been working as a full professor at Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. His current research interests include inorganic-organic hybrid photofunctional materials, infrared nonlinear optical materials, and catalytic materials.

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40843_2022_2417_MOESM1_ESM.pdf

Remarkable Phase-Matchable Second-Harmonic Generation Realized by Strong Polarities of [PbSe3] and [GaSe4] Functional Motifs in PbGa4Se7

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Zheng, ZX., Qiu, ZX., Xie, CH. et al. Remarkable phase-matchable second-harmonic generation realized by strong polarities of [PbSe3] and [GaSe4] functional motifs in PbGa4Se7. Sci. China Mater. 66, 2795–2802 (2023). https://doi.org/10.1007/s40843-022-2417-2

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